79919-48-5Relevant academic research and scientific papers
The bridging sulfide anion reactivity of Roussin's red salt
Seyferth, Dietmar,Gallagher, Michael K.,Cowie, Martin
, p. 539 - 548 (2008/10/08)
Reactions of Roussin's red sodium salt with organic halides gave (μ-RS)2Fe2(NO)4 (two isomers) in good yield, while reactions with R3SnX (R = Ph, Me), Ph3PbBr, and RHgX (R = Ph, Me) and with [η5-C5H5Fe(CO)2THF]BF 4 yielded the expected organometal derivatives. Reactions with (OC)4FeI2 and CpCo(CO)I2 (Cp = η5-C5H6 and η5-C5Me5) gave metal sulfur cluster complexes in low yield. The structure of one of these, (μ3-S)2(η5-C5Me 5Co)2[(ON)2Fe], was determined by X-ray diffraction. Other methods for the preparation of organic and organometallic derivatives of Roussin's red salt were investigated: nitrosylation of the corresponding hexacarbonyl compounds; reaction of (μ-Me3SnS)2Fe2(NO)4 with halides; piperidine-induced Michael additions of (μ-HS)2Fe2(NO)4 to α,β-unsaturated olefins. The complex (η5-C5Me5)2Co 2(μ-S)2Fe(NO)2 crystallizes in the space group C2/c with a = 32.951 (5) A?, b = 8.755 (1) A?, c = 17.619 (2) A?, β = 112.23 (1)°, and Z = 8. Refinement has converged at R = 0.028 and Rw = 0.039 for 262 variables and 3662 unique observations. The structure consists of a trigonal-bipyramidal Co2FeS2 core in which the Co2Fe triangle is capped above and below by triply bridging sulfido groups. One C5Me5 group is bound in an η5-fashion to each Co center and the two partially bent nitrosyls (average Fe-N-O angle = 159.8°) are bound to Fe.
Roussin's red salt revisited: Reactivity of Fe2(μ-E)2(NO)42- (E = S, Se, Te) and related compounds
Rauchfuss, Thomas B.,Weatherill, Timothy D.
, p. 827 - 830 (2008/10/08)
In comparison with Fe2(μ-S)2(CO)62-, Roussin's nitrosyl anion is considerably more stable and is reactive toward a narrower range of electrophiles. These observations are consistent with the view that nitric oxide is a more effective π-acid ligand than carbon monoxide. The net result is that the nucleophilicity of metal nitrosyl complexes is attenuated relative to the analogous carbonyls. An additional finding of this study relates to the synthetic utility of Fe2(μ-I)2(NO)4. This diiron reagent allows one to prepare anhydrous solutions of Fe2(μ-E)2(NO)42- (E = S, Se, Te). These intermediates permit the assembly of organochalcogenide ligands in situ, thus obviating the need for noxious and unstable ligand precursors.
